Showing papers on "Goethite published in 2022"

Hydrogeochemical characteristics, sources and human health risk assessment of heavy metal dispersion in the mine pit water-surface water-groundwater system in the largest manganese mine in Ghana

Abstract: This study was conducted to appraise the hydrogeochemical characteristics and sources of heavy metals and the probable human health risks associated with the consumption of water contaminated with heavy metals in the mine pit water–surface water–groundwater system in the Nsuta manganese mining area in western Ghana. Therefore, a total of 29 samples were collected for hydrochemical analysis and the hydrochemical data was interpreted using multivariate statistical analysis. The results indicate that the pH of water in the mine pit water–surface water–groundwater system is slightly acidic to alkaline in nature. The groundwater evolved from Ca-Mg-SO4, Ca-Mg-HCO3-SO4, Ca-Mg-Na-Cl to Ca-Na-Cl-HCO3 water type with other mixed types, reflecting intense water–rock interaction and dissolution of rocks belonging to the Banded Manganese Formation and the Birimian metasediments in the area. The water is supersaturated with respect to goethite and hematite, pointing to precipitation and dissolution of these minerals. The Water Hazard Index values range from 0.20 to 30.5, implying minimal to extreme toxicity of the water. The mine pit water shows very high Fe, Mn, Ni, As and Sb concentrations, which resulted in hydromorphic dispersion of the heavy metals to the surface water and groundwater. The computed Hazard Index values show higher values (>1) in the surface water and mine pit water, and the carcinogenic risk is low in the groundwater, high in the surface water and extremely high in the mine pit water. Therefore, appropriate control and remedial measures should be urgently put in place to safeguard the health of the people.

Understanding the Importance of Labile Fe(III) during Fe(II)-Catalyzed Transformation of Metastable Iron Oxyhydroxides.

Abstract: Transformation of metastable Fe(III) oxyhydroxides is a prominent process in natural environments and can be significantly accelerated by the coexisting aqueous Fe(II) (Fe(II)aq). Recent evidence points to the solution mass transfer of labile Fe(III) (Fe(III)labile) as the primary intermediate species of general importance. However, a mechanistic aspect that remains unclear is the dependence of phase outcomes on the identity of the metastable Fe(III) oxyhydroxide precursor. Here, we compared the coupled evolution of Fe(II) species, solid phases, and Fe(III)labile throughout the Fe(II)-catalyzed transformation of lepidocrocite (Lp) versus ferrihydrite (Fh) at equal Fe(III) mass loadings with 0.2-1.0 mM Fe(II)aq at pH = 7.0. Similar to Fh, the conversion of Lp to product phases occurs by a dissolution-reprecipitation mechanism mediated by Fe(III)labile that seeds the nucleation of products. Though for Fh we observed a transformation to goethite (Gt), accompanied by the transient emergence and decline of Lp, for initial Lp we observed magnetite (Mt) as the main product. A linear correlation between the formation rate of Mt and the effective supersaturation in terms of Fe(III)labile concentration shows that Fe(II)-induced transformation of Lp into Mt is governed by the classical nucleation theory. When Lp is replaced by equimolar Gt, Mt formation is suppressed by opening a lower barrier pathway to Gt by heterogeneous nucleation and growth on the added Gt seeds. The collective findings add to the mechanistic understanding of factors governing phase selections that impact iron bioavailability, system redox potential, and the fate and transport of coupled elements.

Effect of Agricultural Organic Inputs on Nanoplastics Transport in Saturated Goethite-Coated Porous Media: Particle Size Selectivity and Role of Dissolved Organic Matter

Abstract: The transport of nanoplastics (NPs) through porous media is influenced by dissolved organic matter (DOM) released from agricultural organic inputs. Here, cotransport of NPs with three types of DOM (biocharDOM (BCDOM), wheat strawDOM (WSDOM), and swine manureDOM (SMDOM)) was investigated in saturated goethite (GT)-coated sand columns. The results showed that codeposition of 50 nm NPs (50NPs) with DOM occurred due to the formation of a GT–DOM–50NPs complex, while DOM loaded on GT-coated sand and 400 nm NPs (400NPs) aided 400NPs transport due to electrostatic repulsion. According to the quantum chemical calculation, humic acid and cellulose played a significant role in 50NPs retardation. Owing to its high concentration, moderate humification index (HIX), and cellulose content, SMDOM exhibited the highest retardation of 50NPs transport and promoting effect on 400NPs transport. Owing to a high HIX, the effect of BCDOM on the mobility of 400NPs was higher than that of WSDOM. However, high cellulose content in WSDOM caused it to exhibit a 50NPs retardation ability that was similar to that of BCDOM. Our results highlight the particle size selectivity and significant influence of DOM type on the transport of NPs and elucidate their quantum and colloidal chemical-interface mechanisms in a typical agricultural environment.

Goethite modified biochar simultaneously mitigates the arsenic and cadmium accumulation in paddy rice (Oryza sativa) L

Abstract: Cadmium (Cd) and arsenic (As) contamination of paddy soils is a serious global issue because of the opposite geochemical behavior of Cd and As in paddy soils. Rice plant (Oryza sativa L.) cultivation in Cd- and As- contaminated paddy soil is regarded as one of the main dietary cause of Cd and As entry in human beings. This study aimed to determine the impact of goethite-modified biochar (GB) on bioavailability of both Cd and As in Cd- and As- polluted paddy soil. Contrary to control and biochar (BC) amendments, the application of GB amendments significantly impeded the accumulation of both Cd and As in rice plants. The results confirmed an obvious reduction in Cd and As content of rice grains by 85% and 77%, respectively after soil supplementation with GB 2% amendment. BC 3% application minimized the Cd uptake by 59% in the rice grains as compared to the control but exhibited a little impact on As accumulation in rice grains. Sequential extraction results displayed an increase in immobile Cd and As fractions of the soil by decreasing the bioavailable fractions of both elements after GB treatments. Fe-plaque formation on the root surfaces was significantly variable (P ˂ 0.05) among all the amendments. GB 2% treatment significantly increased the Fe content (10 g kg-1) of root Fe-plaque by 48%, which ultimately enhanced the sequestration of Cd and As by Fe-plaque and minimized the transport of Cd and As in rice plants. Moreover, GB treatments significantly changed the relative abundance of the microbial community in the rice rhizosphere and minimized the metal(loid)s mobility in the soil. The relative abundance of Acidobacteria, Firmicutes and Verrucomicrobia increased with GB 2% treatment while those of Bacteroidetes and Choloroflexi decreased. Our findings confirmed improvement in the rice grains quality regarding enhanced amino acid contents with GB application. Overall, the results of this study demonstrated that GB amendment simultaneously alleviated the Cd and As concentrations in edible parts of rice plant and provided a new valuable method to protect the public health by effectively remediating the co-occurrence of Cd and As in paddy soils.

Iron oxyhydroxide nanoparticles: green synthesis and their cytotoxicity activity against A549 human lung adenocarcinoma cells

Abstract: Iron oxyhydroxide (α-FeOOH, Goethite) is one of the most thermodynamically stable iron oxides and a widespread soil mineral. In this study, a mixture of two phenolic extracts of rosemary and Echinacea was utilized as stabilizing and reducing agents for the synthesis of Goethite (FeOOH) nanoparticles without utilizing harmful toxic solvents. The resulting nanoparticles were characterized by X-ray powder diffraction (XRD), field emission scanning electron microscopy (FESEM)-energy dispersive spectroscopy (EDS), transmission electron microscopy (TEM), vibrating-sample magnetometer (VSM), thermogravimetry/differential thermal analysis (TG/DTA), and Brunauer–Emmett-Teller (BET). MTT assay was applied for evaluating the possible toxicity of the nanoparticles against A549 human lung adenocarcinoma cells.

Phase transformation of Cr(VI)-adsorbed ferrihydrite in the presence of Mn(II): Fate of Mn(II) and Cr(VI)

Abstract: Ferrihydrite is an important sink for the toxic heavy metal ions, such as Cr(VI). As ferrihydrite is thermodynamically unstable and gradually transforms into hematite and goethite, the stability of Cr(VI)-adsorbed ferrihydrite is environmentally significant. This study investigated the phase transformation of Cr(VI)-adsorbed ferrihydrite at different pH in the presence of aqueous Mn(II), as well as the fate of Mn(II) and Cr(VI) in the transformation process of ferrihydrite. Among the ferrihydrite transformation products, hematite was dominant, and goethite was minor. The pre-adsorbed Cr(VI) inhibited the conversion of ferrihydrite to goethite at initial pH 3.0, whereas little amount of adsorbed Mn(II) favored the formation of goethite at initial pH 7.0. After the aging process, Cr species in solid phase existed primarily as Cr(III) in the presence of Mn(II) at initial pH 7.0 and 11.0. The aqueous Mn concentration was predominantly unchanged at initial pH 3.0, whereas the aqueous Mn(II) was adsorbed onto ferrihydrite or form Mn(OH)2 precipitates at initial pH 7.0 and 11.0, promoting the immobilization of Cr(VI). Moreover, the oxidation of Mn(II) occurred at initial pH 7.0 and 11.0, forming Mn(III/IV) (hydr)oxides.

Phase transformation of Cr(VI)-adsorbed ferrihydrite in the presence of Mn(II): Fate of Mn(II) and Cr(VI)

Abstract: Ferrihydrite is an important sink for the toxic heavy metal ions, such as Cr(VI). As ferrihydrite is thermodynamically unstable and gradually transforms into hematite and goethite, the stability of Cr(VI)-adsorbed ferrihydrite is environmentally significant. This study investigated the phase transformation of Cr(VI)-adsorbed ferrihydrite at different pH in the presence of aqueous Mn(II), as well as the fate of Mn(II) and Cr(VI) in the transformation process of ferrihydrite. Among the ferrihydrite transformation products, hematite was dominant, and goethite was minor. The pre-adsorbed Cr(VI) inhibited the conversion of ferrihydrite to goethite at initial pH 3.0, whereas little amount of adsorbed Mn(II) favored the formation of goethite at initial pH 7.0. After the aging process, Cr species in solid phase existed primarily as Cr(III) in the presence of Mn(II) at initial pH 7.0 and 11.0. The aqueous Mn concentration was predominantly unchanged at initial pH 3.0, whereas the aqueous Mn(II) was adsorbed onto ferrihydrite or form Mn(OH)2 precipitates at initial pH 7.0 and 11.0, promoting the immobilization of Cr(VI). Moreover, the oxidation of Mn(II) occurred at initial pH 7.0 and 11.0, forming Mn(III/IV) (hydr)oxides.

Iron from coal combustion particles dissolves much faster than mineral dust under simulated atmospheric acidic conditions

Abstract: Abstract. Mineral dust is the largest source of aerosol iron (Fe) to the offshore global ocean, but acidic processing of coal fly ash (CFA) in the atmosphere could be an important source of soluble aerosol Fe. Here, we determined the Fe speciation and dissolution kinetics of CFA from Aberthaw (United Kingdom), Krakow (Poland), and Shandong (China) in solutions which simulate atmospheric acidic processing. In CFA PM10 fractions, 8 %–21.5 % of the total Fe was found to be hematite and goethite (dithionite-extracted Fe), and 2 %–6.5 % was found to be amorphous Fe (ascorbate-extracted Fe), while magnetite (oxalate-extracted Fe) varied from 3 %–22 %. The remaining 50 %–87 % of Fe was associated with other Fe-bearing phases, possibly aluminosilicates. High concentrations of ammonium sulfate ((NH4)2SO4), often found in wet aerosols, increased Fe solubility of CFA up to 7 times at low pH (2–3). The oxalate effect on the Fe dissolution rates at pH 2 varied considerably, depending on the samples, from no impact for Shandong ash to doubled dissolution for Krakow ash. However, this enhancement was suppressed in the presence of high concentrations of (NH4)2SO4. Dissolution of highly reactive (amorphous) Fe was insufficient to explain the high Fe solubility at low pH in CFA, and the modelled dissolution kinetics suggest that other Fe-bearing phases such as magnetite may also dissolve relatively rapidly under acidic conditions. Overall, Fe in CFA dissolved up to 7 times faster than in a Saharan dust precursor sample at pH 2. Based on these laboratory data, we developed a new scheme for the proton- and oxalate-promoted Fe dissolution of CFA, which was implemented into the global atmospheric chemical transport model IMPACT (Integrated Massively Parallel Atmospheric Chemical Transport). The revised model showed a better agreement with observations of Fe solubility in aerosol particles over the Bay of Bengal, due to the initial rapid release of Fe and the suppression of the oxalate-promoted dissolution at low pH. The improved model enabled us to predict sensitivity to a more dynamic range of pH changes, particularly between anthropogenic combustion and biomass burning aerosols.

Understanding Competitive Phosphate and Silicate Adsorption on Goethite by Connecting Batch Experiments with Density Functional Theory Calculations.

Abstract: Despite the biogeochemical importance of phosphate fate and transport in aquatic environments, little is known about how competition with other common aqueous oxyanions affects its retention by mineral surfaces. Here, we examined the competitive uptake of phosphate and silicate on goethite over a wide pH range, using batch measurements supported by DFT calculations. The results show selective adsorption of phosphate at pH < 4 and silicate at pH > 10 with little to no competitive effect. However, between 4 < pH < 10, the total phosphate and silicate loading was found to be almost equal to that of silicate loading from single-component solution, revealing a proportionate competition for surface site types and a competitive effect controlling their mutual retention. DFT-calculated adsorption energies and charge density redistributions for various surface complexes on different charged (101) and (210) facets are consistent with the trends observed in batch measurements, suggesting that the observed behavior reflects the primary controlling influence of goethite surface chemistry at the molecular scale. An important implication is that at the circumneutral pH in most environmental systems, where iron oxyhydroxides comprise much of the reactive interfacial area, unbound phosphate concentrations may be strongly controlled by dissolved silicate concentration, and vice versa.

Can Weathering of Banded Iron Formations Generate Natural Hydrogen? Evidence from Australia, Brazil and South Africa

Abstract: Oxidation of iron-rich rock is known to generate H2 in oceanic as well as in continental domains. Here we tested the possibility of H2 generation as the result of weathering of banded iron formations (BIF). The BIF constitute more than 60% of global iron ore reserves with low Fe3+/Fetot and total Fe ranging from 20 to 40 wt% and are therefore good candidates for H2 production potential. In the vicinity of BIF-hosted iron mines in Australia, Brazil and South Africa, satellite imaging has revealed the presence of sub-circular depressions that usually are the proxy of H2-emitting features. A morphological comparison of the sub-circular depressions with the ones observed in previous studies point to probable H2 seeping in these areas. In parallel, a petrological study conducted on altered and fresh BIF samples from the Hamersley Province in Western Australia also suggests H2 generation during BIF weathering. Indeed, mineral transitions from ferrous silicate (riebeckite and/or minnesotaite) to ferric iron oxi-hydroxides (goethite) or from ferrous and ferric oxides (magnetite) to exclusively ferric oxides (maghemite, hematite, goethite) were observed on the samples. The oxidation of ferrous iron by aqueous fluids circulating through and leaching the BIF is promising for H2 generation. The BIF weathering profile suggests that the limiting factor is the presence of water, and that this reaction is happening at, or near, surface temperature. This challenges the idea that high temperatures are required to generate H2 as it is the case during the serpentinization. The link between BIF and H2 will have however to be further investigated to better constrain the reactions and their kinetics.